Regioselective Cage Opening of La sub(2)[at]D sub(2)(10611)-C sub(72) with 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazine
The thermal reaction of the endohedral metallofullerene La sub(2)[at]D sub(2)(10611)-C sub(72), which contains two pentalene units at opposite ends of the cage, with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine proceeded selectively to afford only two bisfulleroid isomers. The molecular structure of on...
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Published in | Angewandte Chemie Vol. 127; no. 7; pp. 2260 - 2263 |
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Main Authors | , , , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
01.02.2015
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Subjects | |
Online Access | Get full text |
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Summary: | The thermal reaction of the endohedral metallofullerene La sub(2)[at]D sub(2)(10611)-C sub(72), which contains two pentalene units at opposite ends of the cage, with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine proceeded selectively to afford only two bisfulleroid isomers. The molecular structure of one isomer was determined using single-crystal X-ray crystallography. The results suggest that the [4+2] cycloaddition was initiated in a highly regioselective manner at the C--C bond connecting two pentagon rings of C sub(72). Subsequent intramolecular electrocyclization followed by cycloreversion resulted in the formation of an open-cage derivative having three seven-membered ring orifices on the cage and a significantly elongated cage geometry. The reduction potentials of the open-cage derivatives were similar to those of La sub(2)[at]D sub(2)-C sub(72) whereas the oxidation potentials were shifted more negative than those of La sub(2)[at]D sub(2)-C sub(72). These results point out that further oxidation could occur easily in the derivatives.Original Abstract: Fullerene im OP: Die thermische Reaktion des endohedralen Metallofullerens La sub(2)[at]D sub(2)(10611)-C sub(72) mit 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazin liefert selektiv nur zwei Bisfulleroid-Isomere. Die Rontgen-kristallographische Analyse eines Isomers (siehe Bild) belegt die Bildung eines geoffneten Derivats mit drei siebengliedrigen Ringen und laenglichem Kaefig. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 content type line 23 ObjectType-Feature-2 |
ISSN: | 0044-8249 1521-3757 |
DOI: | 10.1002/ange.201410012 |